Process for uniformly waving damaged hair



United States Patent 3,395,216 PROCESS FOR UNIFORMLY WAVING DAMAGED HAIRRobert Allen Wall, Darien, and Percy Fainer, Ridgefield, Conn.,assignors to Clairol Incorporated, New York, N.Y., a corporation ofDelaware No Drawing. Filed Nov. 9, 1964, Ser. No. 410,000 6 Claims. (Cl.424-72) ABSTRACT OF THE DISCLOSURE A process for uniformly wavingpreviously damaged hair resulting in non-uniformly porous hair whichinvolves pre-treating the hair with an aqueous acidic oxidizing agentcapable of arresting the waving action of a waving composition, e.g.,aqueous alkaline thioglycollic acid, and thereafter subjecting said hairto the action of said thioglycollic acid composition, whereby the hairis given a uniform wave.

This invention relates to a process for safely imparting a uniformpermanent wave to unduly porous hair, and particularly to non-uniformlyporous hair. This porosity and non-uniformity of porosity may resultfrom earlier bleaching treatments or tinting with oxidation dyecompositions or other hair treatments or conditions which tend to damagehair.

Living hair which has been bleached requires periodic treatment to takecare of the new hair growth that occurs at the root section of the hair,i.e., the section of the hair strand closest to the scalp. Thistreatment, known as the retouch process, involves the application ofbleach near said root section for the purpose of giving the new growththe same color as the previously bleached portions of the hair, so as togive the whole head a uniform color. Although this treatment is designedto bleach only the new hair growth, it invariably also results insubjecting already bleached hair to an additional bleaching action. Asthe process is repeated, portions of the hair receive a different numberof multiple bleaching treatments.

In the treatment of hair known in this art as tinting with oxidationdyes a dye is applied to the hair whose color development requires theaction of an oxidizing agent which is generally kept separate from thedye until the dye is applied to the head. Although the function of theoxidizing agent in this instance is not primarily to bleach hair, itspresence on the hair serves to effect the hair in substantially thesimilar manner as it was added simply for the purpose of bleaching thehair. Thus, repeated tinting of hair with oxidation dye compositions issubstantially equivalent in effect to multiple bleaching treatmentsinsofar as this invention is concerned.

One effect of multiple bleaching treatments of hair is to increase theporosity and damage of the hair, the degree of porosity and damage beinga function of the number of bleaching treatments that the particularhair section has been subjected to. By continual retouching the porosityof the hair changes and is made non-uniform so that it may beprogressively more porous from the root section to the end section ofthe hair. A similar condition results from multiple tintings withoxidation dye composition. This phenomenon complicates the cold wavingprocess of bleached hair.

Cold waving of hair is generally effected by winding hair on a curlerand then applying a waving lotion which employs a reducing agent as theprincipal active ingredient (e.g., dilute alkaline thioglycollic acidsolution). After a suitable period of time (usually 10 minutes), thehair, while still on the roller, is rinsed with water, towel blotted andtreated with an oxidative neutralizing agent which 3,395,216 PatentedJuly 30, 1968 "ice stops the action of the waving lotion (and, accordingto generally accepted theory, restores the disulfide bonds ruptured bythe waving lotion). After about 5 minutes, the hair is rinsed, thecurlers removed and the hair set. The degree to which a section of ahair strand will be waved is dependent on the amount of waving lotionthat gets into it which in turn is a function of the porosity of theparticular hair section. Thus, for any given concentration of wavelotion, all other things being equal, the more porous hair is given agreater wave and the less porous hair is given a lesser wave.

Moreover, non-uniformly porous hair, as for example, hair that has beenbleached and subjected to one or more retouching treatments or subjectedto multiple tintings with oxidation dye compositions, cannot beuniformly waved using the prior art techniques. Thus, for instance, if awaving lotion designed for use on bleached hair, i.e., hair having agreater porosity than unbleached hair, is employed, it is found that theend sections of the hair are well-waved, whereas the root sections ofthe hair are only weakly waved. If waving solutions are utilized whichare strong enough to wave the root sections of the bleached hair, i.e.,the new hair growth, there results an over-processing and severe hairdamage and breakage at the end section or more porous sections of thehair.

It has now been found, in accordance with the present invention, thatthe above difficulties can be avoided by pretreating the non-uniformlyporous hair, produced by prior bleaching treatments, prior tinting withoxidation dye compositions or otherwise, with a pre-neutralizing agentfor a hair waving composition and then applying said hair wavingcomposition in ordinary strength to obtain the desired uniform wave.

As used herein, the term pm-neutralizing agent describes a neutralizingagent that is applied to the hair prior to the application of the hairwaving composition and is to be distinguished from the finalneutralizers applied after the application of the hair wavingcomposition.

It is accordingly an object of the present invention to provide aprocess for safely imparting a uniform wave to non-uniformly poroushair, such as hair subjected to pre vious bleaching treatment ortreatments or tintings with oxidation dye compositions.

It is also an object of the present invention to provide a process forsafely imparting a uniform wave to nonuniformly porous hair, e.g.,previously bleached hair or hair tinted with oxidation dye compositions,which can be effected through the use of a single waving solutionregardless of the degree of porosity or non-uniformity of porosity ofthe hair.

-It is a further object of the present invention to provide a processfor safely imparting a uniform wave to nonuniformly porous hairresulting from previous bleaching and retouching treatments or oxidationdye composition treatments which involves pretreating the hair with apreneutralizing agent for a cold hair waving solution prior to theapplication of the cold hair waving solution.

Other and more detailed objects of this invention will become apparentfrom the following description and claims.

As mentioned above, the process of the present invention is ofparticular use in the connection with hair damaged by previous bleachingtreatments or tinting treatments employing oxidation dye compositions.Any of the known hair bleaching compositions and oxidation dyehair-tinting compositions will produce the undue porosity of hairmentioned supra. Typical hair bleaches which will bring this conditionabout are shown in Cosmetics, Science and Technology by Edward Sagarin(1957), pages 480 through 484. Similarly, typical oxidation dyecompositions which will bring about said hair 3 damage is also shown inSagarins book on pages 503 through 512.

To illustrate the comparative merits of the present process as comparedwith prior art processes, the experimental development of porous hairthrough the use of a hair bleach or a tinting oxidation dye compositionis desirable. For this purpose two compositions identified below as (A)Hair Bleach Composition or (B) Tinting Oxidation Dye Composition wereprepared. Hair which is referred to herein as bleached hair is hairwhich has been treated with composition (A). Hair referred to as tintedhair is hair which has been treated with composition (B).

(A) Hair bleach composition Component (a): Percent Oleic acid 24 TritonX-15 (glycol ether of p-ter. acetylphenol) 13 Igepal CA. 630(octylphenoxy polyethoxyethanol average M.W. 646 25 NH (as 28% NH;, in HO) 2 Isopropanol 15 Propylene glycol 15 H O 6 Component (b):

Aqueous H 6 Component (c) (accelerator) Ammonium persulfate 17 Potassiumpersulfate 67 Sodium silicate 11 Sodium carbonate 5 In use 2 ounces ofcomponent (a), 4 ounces of component (b) and about 21 grams of component(c) are mixed together and applied to the hair for l-2 hours, unlessotherwise specified.

(B) Tinting oxidation dye composition Component (a).Same as component(a) in composition (A) above, except that it contains 3.75%pphenylenediamine, .06% 1,S-dihydroxynaphthalene, .05p-aminodiphenylamine. In place of the 6% water, 2.14% water is used.

Component (b).6% aqueous H 0 In use 2 ounces of component (a) and 2ounces of component (b) are mixed together and applied to the hair andleft in contact therewith for 30-60 minutes.

It is current practice with commercial permanent wave preparation torecommend alkaline thioglycollate permanent waving lotions of variousstrengths depending on the degree of damage of the hair to be waved;lower strength solutions being recommended for hair having the greaterdegree of damage. In general, decreasing strength of the waving lotionsis accomplished by lowering the thioglycollic acid concentration alongwith the alkalinity.

Exampes of three typical commercial waving lotions are given in Table I:

TABLE I Percent Waving Lotion Percent NH; Thioglycollic Acid N forNormal Hair 2.0 7. 6 T for Oxidation Dye Tinted Hair 1.0 3. 8 B forBleached Hair 0. 5 1. 9

are referred to as Shaft and Ends respectively. The hair sample employedwas normal brown hair and the number of bleaches that each type of hairwere subjected to is as follows:

Root-1 two-hour bleach. Shaft2 two-hour bleaches. Ends-3 two-hourbleaches.

The wet waving elliciency (see Proc. Sci. Sec. TGA, Dec. 1956, p. 12)and the strength of the hair was determined. The latter is expressed inarbitrary strength units related to the tensile modu1usthe higher thenumber, the greater the hair strength. The results obtained are shown inTable II:

These results show the non-uniformity in waving efficiency obtained withboth the lotion for bleached and for tinted hair. In addition, thehigher degree of damage imparted to the ends by the lotion for tintedhair is shown.

In contrast to the current commercial practice which requires a wavinglotion of different strength for hair of different degrees of damage,the present invention makes it possible to use a single waving lotion orother waving composition to wave any hair regardless of its degree ofdamage and the non-uniformity of its porosity. As mentioned above, thisis accomplished by pretreating the hair to be waved with apre-neutralizing agent for the cold waving composition to be employed.This pretreatment may then be followed by the application of the coldwaving composition and technique.

The term pre-neutralizing agent as employed herein is not used in itslimited sense to only designate an agent whose function is merely tochange the pH of waving compositions. It is used rather in its broadsense to designate any material which has a tendency to arrest the hairwaving action of the waving composition that is to be subsequentlyapplied. The mechanism of this arrest may involve: (a) a change in pH tothe acid side, (b) oxidation of the active component of the wavingcomposition, (0) a combination of (a) and (b), (d) dilution of thewaving lotion, etc.

The particular pre-neutr-alizing agent or agents that are employed inaccordance with the present invention need not be of any special type.Their selection will of course depend on the nature of the hair wavingcomposition which is to be subsequently used. In general, however, thepre-neutralizing agent will be of the oxidizing type and will functionby the oxidation of the active components of the waving composition toan inactive form. A variety of neutralizing agents of the oxidizing typewhich may serve as pre-neutralizing agents are known in the prior artand maybe used in this invention. Typical among these are those shown inCosmetics, Science and Technology, by Edward Sagarin, IntersciencePublishers, Inc., New York, 1957, pages 617 through 620. These includehydrogen peroxide, alkali-metal bromates, alkalimetal perborates,alkali-metal chlorites, urea peroxides, combinations thereof, etc.

In the preferred form of this invention, the pre-neutralizing agent willbe of the acidic oxidation type. This will function as an oxidizingagent and also serve to reduce the pH of the hair waving composition toarrest the action of the latter. Solutions of any persulfate or bromateoxidizing agent having a pH below 7 are particularly suitable for thispurpose. By way of example the following may be mentioned: ammoniumpersulfate, potassium persulfate, sodium bromate, potassium bromate.

The quantity of pre-neutralizing agent that may be contained in thepre-neutralizing composition can vary over a wide range, depending onwhether the hair to be waved is bleached or tinted with oxidation dyecompositions, and on the strength of the waving lotion chosen for use.In most cases, however, it will take the form of an aqueous solution ofan oxidizing agent containing from 0.5 to 5.0% active oxygen having a pHbetween 3.5 and 7.0. In addition, it may also contain other ingredientssuch as wetting agents, thickeners, opacifiers, perfume oils,preservatives, stabilizers, film formers, hair conditioners, etc.

Hair waving compositions containing a reducing agent as the principalactive ingredient are most suitable for use with the present invention.Of particular utility are solutions of thioglycollic acid or itsderivatives (e.g. amides, esters, etc.) having a pH in the range of 7.0to 9.4 and a concentration of reducing agent expressed in terms ofthioglycollic acid ranging from 0.5 to 9.0%. These solutions may containas the alkali any of the following, either alone or in combination witheach other, e.g., ammonia, alkali-metal cations, alkaline earth cations,primary, secondary or tertiary amines (e.g. ethylamine, diethylamine,triethylamine), primary, secondary or tertiary alkanolamines (e.g.,monoethanola-mine, diisopropanol-amine, triethanolamine), or cyclicamines, such as morpholine.

It is further to be understood that the present invention is applicableto hair waving compositions which comprise simple aqueous solutions ofthe active hair-Waving agent, as well as more elegant compositions whichmay contain opacifiers, emulsifiers, perfumes, thickening agents, filmformers, hair conditioners mentioned above.

In the practice of the present invention, hair previously bleached andretouched or subjected to multiple tintings with oxidation dyecompositions so as to render the hair non-uniformly porous is pretreatedwith the p-re-neutralizing agent, preferably in the form of an aqueoussolution. The time of treatment may vary, depending upon the agent used.In general, the treatment will last from 1 to 20 minutes and preferablyfor about minutes.

The hair so treated may then be given a usual cold hair waving treatmentusing any of the above-mentioned hair waving agents. This treatment mayalso vary between 1 and minutes. However, it will usually last 10minutes. The hair is then rinsed and neutralized according to prior artpractices.

Although applicants do not want to be bound by any theory of action, themanner in which the present invention is thought to operate is set forthbelow. Because of the non-uniformity in the porosity of hair which hasbeen subjected to multiple bleaching operations or tintings withoxidation dye compositions, the pre-neutralizing agent is absorbed intothe hair structure in different amounts in diiferent sections of thehair.

In most cases the greatest absorption takes place at the end section ofthe hair and the least absorption takes place at the root section. Whenthe cold waving solution is applied, it is subjected to the greatestdegree of neutralization in those hair sections which have absorbed themost pro-neutralizing agent. At any one site, however, there is moreWaving lotion than pro-neutralizing agent so that waving of the hair canbe effected. The result is a more level overall wave without damage tothe more porous sections of the hair, i.e. the end sections.

The above has been verified experimentally by the following experiments:

Hair bleached to resemble root, shaft and ends, as described above, wastreated with 3% aqueous ammonium persulfate for 10 minutes. It was thenwaved out in the usual manner mentioned supra for about 10 minutes usingwaving lotion T described in Table I above and neutralized with a 12%aqueous solution of sodium bromate. The wet waving efiiciencies andstrengths were determined. The results are shown in Tables III and IV.

TABLE III.-COMPARISON OF WET WAVING EFFICIENCY USING WAVING LOTION T ASDESCRIBED ABOVE Hair Used Pretreated Hair Non-Pretreated Hair Root 55 Shalt. 70 Ends 55 Lotion B diluted half strength:

Non-pretreated hair 13 Table IV illustrates the increase in hairstrength that attends the practice of the present invention, the highernumber indicating the greater strength. In the first two columns therelative strength of hair waved with lotion B, described in Table I, isset forth. The hair in Column 1 was first pretreated with 3% aqueousammonium persulfate for 10 minutes in accordance with this invention.The hair in Column 2 was given no such pretreatment. The increase inhair strength is obvious. Column 3 shows that hair which has not beenpretreated in accordance with the present invention is not as strong ashair treated in accordance with the present invention, even when theWaving lotion applied to the former is half the strength of that appliedto the latter.

Practical bleached and oxidation dye tinted head tests confirmed theabove data. A commercial permanent wave for bleached hair was compared,by half-head tests, with the method of pretreating the hair withammonium persulfate followed by waving with a lotion for tinted hair andneutralizing in the accepted manner. The following results wereobtained:

Pretreatment process: Commercial 1) Uniform wave Tight wave at the ends.(2) Soft feel when dry Harsh feel when dry. (3) Firm when wet Mushy whenwet. (4) No breakage on comb out Breakage on comb out.

Similar results were obtained with the following basic systems onbleached hair:

(1) Pretreatment solution, 1.5% aqueous solution of ammonium persulfate.Waving lotion, 6.4% aqueous solution of thioglycollic acid +2% NH Lotionadjusted to a pH of 7.8 with acetic acid.

(2) Pretreatment solution, 3.0% aqueous solution of ammonium persulfate.Waving lotion, 8.7% aqueous solution of thioglycollic acid +25% NHLotion adjusted to pH 7.8 with acetic acid.

Similar comparative results were obtained with half head tests conductedon tinted heads with the following basic systems:

(1) Pretreatment solution, 1.5% aqueous solution of ammonium persulfate.Waving lotion, 5.0% aqueous solution of thioglycollic acid +12% NH pHadjusted to 9.2 with sodium hydroxide.

(2) Pretreatment solution, 1.5% aqueous solution of ammonium persulfate.Waving lotion, 5.0% aqueous solution of thioglycollic acid +33%monoethanolamine +05% NH pH 9.1-9.2.

In Table V below are given three additional examples of basic wavinglotion formula which may be used in connection with the pro-neutralizingtreatment on bleached hair. Each of the lotions is an aqueous solutioncontaining the amount and ingredients indicated.

In Table VI below are given two additional examples of basic wavinglotion formula which may be used in connection with the preneutralizingtreatment on tinted hair. Each waving lotion is likewise an aqueoussolution containing the amount and ingredients indicated.

TABLE VI Percent Percent Percent Percent I N11 ThioglycollicMonoethanolamlne Trlethanolamlne pH Acid Although. the invention hasbeen described with reference to specific forms thereof, it will beunderstood that many changes and modifications may be made withoutdeparting from the spirit of this invention.

What is claimed is:

1. A process for uniformly waving non-uniformly porous hair resultingfrom previous bleaching treatments which comprises pretreating saidbleached hair with a dilute aqueous composition of an acidic oxidizingagent selected from the group consisting of ammonium persulfate,potassium persulfate, sodium bromate and potassium bromate and mixturesthereof, and subsequently subjecting said pretreated hair to the coldwaving action of an aqueous alkaline composition of thioglycollic acid,whereby said hair is given a uniform wave.

2. A process according to claim 1 including the step of applying anoxidative neutralizing agent to said hair subsequent to the applicationof the hair waving composition whereby the action of the latter isarrested.

3. A process for uniformly waving non-uniformly porous hair resultingfrom previous treatment with a tinting oxidation dye compositioncontaining an oxidizing agent which comprises pretreating saidpreviously tinted hair with a dilute aqueous composition of an acidicoxidizing agent selected from the group consisting of ammoniumpersulfate, potassium persulfate, sodium bromate, potassium bromate andmixtures thereof and subsequently subjecting said pretreated hair to thecold waving action of an aqueous alkaline solution containingthioglycollic acid, whereby said hair is given a uniform wave.

4. A process according to claim 3 including the step of applying anoxidative neutralizing agent to said hair subsequent to the applicationof said hair waving composition whereby the action of the latter isarrested.

5. A process for uniform waving non-uniformly porous hair resulting fromprevious bleaching treatments which comprises prc-trcating said bleachedhair with a dilute aqueous composition of an oxidizing agent selectedfrom the group consisting of hydrogen peroxide, alkalimetal bromates,alkali-metal perborates, alkali-metal chlorites, urea peroxides andmixtures thereof, and subsequently subjecting said pre-treated hair tothe cold waving action of an aqueous alkaline composition ofthioglycollic acid, whereby said hair is given a uniform wave.

6. A process for uniformly waving non-uniformly porous hair resultingfrom previous treatment with a tinting oxidation dye compositioncontaining an oxidizing agent which comprises pre-treating saidpreviously tinted hair with a dilute aqueous composition of an oxidizingagent selected from the group consisting of hydrogen peroxide,alkali-metal bromates, alkali-metal perborates, alkali-metal chlorites,urea peroxides and mixtures thereof, and subsequently subjecting saidpro-treated hair to the cold waving action of an aqueous alkalinesolution containing thioglycollic acid, whereby said hair is given auniform wave.

References Cited UNITED STATES PATENTS 2,892,756 6/1959 Flesch 167-87.13,098,694 7/1963 Reider 167--87.1 X 3,063,908 11/1962 Kalopissis167--87.1 3,106,440 10/1963 Lcwin 8128 ALBERT T. MEYERS, PrimaryExaminer.

V. C. CLARKE, Assistant Examiner.

